Dppf‐Ligated Palladium Complex as an Efficient Catalyst for the Synthesis of Biaryl Ketones Using Co₂(CO)₈ as a C1 Source with High TON and TOF

Abstract

In this reports, we have synthesized and characterized the palladium catalyst [Pd2(dppf)2(SC12H8S)]2(OTf)4 which is successfully applied for Carbonylative Suzuki‐Miyaura cross‐coupling reaction. Synthesized catalyst was characterized by various analytical techniques such as 1H NMR, 31P NMR, CHNS, and single crystal X‐ray diffraction. The use of Co2(CO)8 as a C1 source instead of gaseous CO is an additional advantage of the developed protocol. The current protocol showing excellent catalytic activity at ppm level of “Pd” concentration to provided high TON and TON. TON could be achieved up to 104 and TOF up to 103. The protocol could tolerate a variety of functional groups and provided wide substrate scope including Heteroaryl ketones. The practical applicability of the proposed protocol up to gram level with marginal loss of the yield of the product. Remarkably, we have synthesized (4‐methoxyphenyl) (3,4,5‐trimethoxyphenyl)methanone and oxybenzone which is pharmaceutically active drug molecules under co‐catalyst, and additive free condition. .

Advances in Transition‐Metal Catalyzed Carbonylative Suzuki‐Miyaura Coupling Reaction: An Update

“…Recently, Bhanage co‐workers [35] also accounted the utilization of sub‐stoichiometric quantity of transition‐metal carbonyl, Co 2 (CO) 8 as environmentally benign C1 source for the carbonylative coupling reactions. The authors showed the method as simple reaction setup and simple extraction process of the product.…”

Xantphos‐coordinated palladium dithiolates: Highly efficient catalyst for decarboxylative Sonogashira reaction into corresponding alkynes

“…[ 36 ] However, owing to the larger bite angle, Xantphos‐capped Pd dithiolate complexes exhibited better catalytic activity in Suzuki [ 36 ] and Heck [ 37 ] cross‐coupling reactions compared with dppe analogue [ 38,39 ] and offered a high turn‐over number (TON). Besides, these stable and highly soluble complexes provided excellent catalytic activity in carbonylative Suzuki–Miyaura reactions [ 40,41 ] as well as in amino and phenoxycarbonylation. [ 42 ] However, organochalcogen ligated palladium catalysts have rarely been reported for Csp–Csp 2 cross‐coupling reaction, [ 43,44 ] in particular for decarboxylative Sonogashira cross‐coupling reaction.…”

Catalytic activity of Pd dithiolate complexes with large‐bite‐angle diphosphines in Heck coupling reactions

“…Macrocyclic Pd complexes of Xantphos exhibited excellent activity with high turnover number (TON) in Suzuki C–C coupling reactions compared to the dppe analogues; moreover they also showed good activity in carbonylative Suzuki–Miyaura reactions . Motivated by the above considerations, we decided to evaluate the catalytic activity of our Xantphos‐capped Pd dithiolate complexes in Heck coupling reactions of styrene and aryl halides.…”